US7160848B2 - Polymers and laundry detergent compositions containing them - Google Patents

Polymers and laundry detergent compositions containing them Download PDF

Info

Publication number
US7160848B2
US7160848B2 US10/734,756 US73475603A US7160848B2 US 7160848 B2 US7160848 B2 US 7160848B2 US 73475603 A US73475603 A US 73475603A US 7160848 B2 US7160848 B2 US 7160848B2
Authority
US
United States
Prior art keywords
detergent composition
polymer
vinyl pyrrolidone
vinyl
detergency
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related, expires
Application number
US10/734,756
Other versions
US20040127390A1 (en
Inventor
Donna Macnab
Catherine Marie-Joseph Soret
Robert Kemeys Thomas
Albert van der Wal
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel IP and Holding GmbH
Original Assignee
Unilever Home and Personal Care USA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Home and Personal Care USA filed Critical Unilever Home and Personal Care USA
Assigned to UNILEVER HOME & PERSONAL CARE USA, DIVISION OF CONOPCO, INC. reassignment UNILEVER HOME & PERSONAL CARE USA, DIVISION OF CONOPCO, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: THOMAS, ROBERT KEMEYS, MACNAB, DONNA, SORET, CATHERINE MARIE-JOSEPH SIMONE, VAN DER WAL, ALBERT
Publication of US20040127390A1 publication Critical patent/US20040127390A1/en
Application granted granted Critical
Publication of US7160848B2 publication Critical patent/US7160848B2/en
Assigned to THE SUN PRODUCTS CORPORATION reassignment THE SUN PRODUCTS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CONOPCO, INC.
Assigned to U.S. BANK NATIONAL ASSOCIATION reassignment U.S. BANK NATIONAL ASSOCIATION SECOND LIEN GRANT OF SECURITY INTEREST IN PATENT RIGHTS Assignors: SPOTLESS ACQUISITION CORP., SPOTLESS HOLDING CORP., THE SUN PRODUCTS CORPORATION (F/K/A HUISH DETERGENTS, INC.)
Assigned to THE SUN PRODUCTS CORPORATION (F/K/A HUISH DETERGENTS, INC.), SPOTLESS ACQUISITION CORP., SPOTLESS HOLDING CORP. reassignment THE SUN PRODUCTS CORPORATION (F/K/A HUISH DETERGENTS, INC.) RELEASE BY SECURITY PARTY AS PREVIOUSLY RECORDED ON REEL 029816 FRAME 0362 Assignors: U.S. BANK NATIONAL ASSOCIATION
Assigned to JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT reassignment JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT SECURITY AGREEMENT Assignors: THE SUN PRODUCTS CORPORATION
Assigned to THE SUN PRODUCTS CORPORATION reassignment THE SUN PRODUCTS CORPORATION RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: JPMORGAN CHASE BANK, N.A.
Assigned to Henkel IP & Holding GmbH reassignment Henkel IP & Holding GmbH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: THE SUN PRODUCTS CORPORATION
Expired - Fee Related legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0036Soil deposition preventing compositions; Antiredeposition agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention relates to laundry detergent compositions containing certain vinyl pyrrolidone copolymers.
  • the compositions exhibit improved detergency on oily and clay soils and reduced soil redeposition during the wash.
  • Polyvinyl pyrrolidone (PVP) and some related polymers are known ingredients of laundry detergent compositions, providing the benefit of reduced dye transfer between fabrics in a mixed load.
  • Laundry detergent compositions containing PVP as a dye transfer inhibitor are disclosed, for example, in WO 92 18597A and WO 95 27028A (Procter & Gamble).
  • GB 1 354 498 discloses laundry detergent compositions containing vinyl pyrrolidone/vinyl acetate (PVP/VA) random copolymers as antiredeposition agents. PVP itself is stated to be ineffective.
  • the present invention provides a laundry detergent composition
  • a laundry detergent composition comprising an organic surfactant, and a hydrophobically modified vinyl pyrrolidone polymer which is a copolymer having a vinyl pyrrolidone backbone and pendant hydrophobic side chains comprising alkyl chains containing from 4 to 20 carbon atoms, the polymer being present in an amount effective to improve detergency and/or antiredeposition.
  • the invention provides the use of a hydrophobically modified vinyl pyrrolidone polymer to improve the detergency and/or antiredeposition of a laundry detergent composition.
  • the polymer used in the detergent compositions of the invention is a polyvinyl pyrrolidone modified by the inclusion of hydrophobic units as pendant side chains.
  • the polymer is a copolymer of vinyl pyrrolidone (VP), providing the polymer backbone, and a hydrophobic monomer.
  • the hydrophobic side chains preferably comprise alkyl chains containing from 4 to 20 carbon atoms.
  • the polymer is an alkylated vinyl pyrrolidone polymer wherein the alkyl chains contain from 4 to 20 carbon atoms.
  • the hydrophobic side chains are derived from a hydrophobic comonomer which is an olefin containing from 4 to 20 carbon atoms.
  • the polymer contains from 10 to 90 mole % of vinyl pyrrolidone (VP) units and from 10 to 90 mole % of hydrophobic comonomer units.
  • VP vinyl pyrrolidone
  • Suitable polymers are commercially available from International Specialty Products (ISP) as the Ganex (Trade Mark), Antaron (Trade Mark) and Agrimer (Trade Mark) series. They may be prepared by chemical modification of PVP with long-chain alpha-olefins. Examples are shown in the Table below.
  • the hydrophobically modified vinyl pyrrolidone polymer has pendant hydrophobic side chains which are alkyl chains having from 4 to 20 carbon atoms linked to the vinyl pyrrolidone backbone by an ester linkage.
  • the hydrophobic monomer precursor of the side chains is preferably a vinyl ester of the general formula I: R 1 —CO—O—CH ⁇ CH 2 (I) wherein R 1 is a linear or branched alkyl group having from 4 to 16 carbon atoms.
  • R 1 is preferably a linear or branched alkyl group having from 6 to 10 carbon atoms.
  • R 1 is a group of the formula II
  • R 2 is a linear alkyl group having from 2 to 8 carbon atoms and R 3 is a methyl or ethyl group.
  • hydrophobic comonomer of the formula I is vinyl 2-ethylhexanoate:
  • the polymer preferably contains from 90 to 99.5 wt % of vinyl pyrrolidone monomer units and from 0.5 to 10 wt % of vinyl 2-ethyl hexanoate monomer units.
  • Copolymers of vinyl pyrrolidone and vinyl 2-ethylhexanoate have the general formula III
  • These polymers may be prepared by free radical polymerisation.
  • the polymer is present in an amount sufficient to enhance detergency and/or antiredeposition.
  • the polymer is present in an amount of from from 0.5 to 5 wt %, preferably from 1 to 4 wt %.
  • the detergent composition may suitably comprise:
  • the pH of the detergent composition is suitably in the range of from 7.0 to 11.0, preferably 7.5 to 10.5. During the wash in dilute form the pH of the detergent composition is from 7 to 11, preferably from 8.0 to 10.5.
  • compositions of the invention may contain any organic surfactants (detergent-active compounds) suitable for incorporation into laundry detergent compositions.
  • Detergent-active compounds may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
  • Many suitable detergent-active compounds are available and are fully described in the literature, for example, in “Surface-Active Agents and Detergents”, Volumes I and II, by Schwartz, Perry and Berch.
  • the preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
  • the total amount of surfactant present is suitably within the range of from 5 to 60 wt %, preferably from 5 to 40 wt %.
  • Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonaites having an alkyl chain length of C 8 –C 15 ; primary and secondary alkylsulphates, particularly C 8 –C 20 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 –C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 –C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
  • Cationic surfactants that may be used include quaternary ammonium salts of the general formula R 1 R 2 R 3 R 4 N + X ⁇ wherein the R groups are long or short hydrocarbyl chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising anion (for example, compounds in which R 1 is a C 8 –C 22 alkyl group, preferably a C 8 –C 10 or C 12 –C 14 alkyl group, R 2 is a methyl group, and R 3 and R 4 , which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
  • R 1 is a C 8 –C 22 alkyl group, preferably a C 8 –C 10 or C 12 –C 14 alkyl group
  • R 2 is a methyl group
  • R 3 and R 4 which may be the same or different, are methyl or
  • the composition comprises a sulphonate anionic surfactant.
  • the sulphonate anionic surfactant comprises linear alkylbenzene sulphonate (LAS).
  • the compositions contains from 3 to 30 wt %, more preferably from 10 to 25 wt %, of LAS.
  • the detergent compositions of the invention also contain one or more detergency builders.
  • the total amount of detergency builder in the compositions may suitably range from 5 to 80 wt %, preferably from 10 to 60 wt %.
  • Preferred builders are alkali metal aluminosilicates, more especially crystalline alkali metal aluminosilicates (zeolites), preferably in sodium salt form.
  • zeolites crystalline alkali metal aluminosilicates
  • Zeolite builders may suitably be present in a total amount of from 5 to 60 wt %, preferably from 10 to 50 wt %.
  • the zeolites may be supplemented by other inorganic builders, for example, amorphous aluminosilicates, or layered silicates such as SKS-6 ex Clariant.
  • the zeolites may be supplemented by organic builders, for example, polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts.
  • polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers
  • monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and
  • compositions of the invention may contain phosphate builders, for example, sodium tripolyphosphate.
  • organic builders are citrates, suitably used in amounts of from 1 to 30 wt %, preferably from 2 to 15 wt %; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt %.
  • Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
  • the detergency builder which is present in an amount of from 5 to 80 wt %, preferably from 10 to 60 wt %, is selected from sodium tripolyphosphate, zeolites, sodium carbonate and mixtures thereof.
  • Detergent compositions according to the invention may also suitably contain a bleach system.
  • a bleach system Preferably this will include a peroxy bleach compound, for example, an inorganic persalt or an organic peroxyacid, capable of yielding hydrogen peroxide in aqueous solution.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate, the latter being especially preferred.
  • the sodium percarbonate may have a protective coating against destabilisation by moisture.
  • the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt %, preferably from 10 to 25 wt %.
  • the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
  • the bleach precursor is suitably present in an amount of from 1 to 8 wt %, preferably from 2 to 5 wt %.
  • Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
  • An especially preferred bleach precursor suitable for use in the present invention is N,N,N′,N′-tetracetyl ethylenediamine (TAED).
  • a bleach stabiliser may also be present.
  • Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA), diethylenetriamine pentaacetate (DTPA), ethylenediamine disuccinate (EDDS), and the polyphosphonates such as the Dequests (Trade Mark), ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphate (DETPMP).
  • compositions of the invention may contain alkali metal, preferably sodium, carbonate, in order to increase detergency and ease processing.
  • alkali metal preferably sodium, carbonate
  • Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt %, preferably from 2 to 40 wt %.
  • sodium silicate may also be present.
  • the amount of sodium silicate may suitably range from 0.1 to 5 wt %.
  • Sodium silicate, as previously indicated, is preferably introduced via the second base granule.
  • Powder flow may be improved by the incorporation of a small amount of a powder structurant.
  • powder structurants include, for example, fatty acids (or fatty acid soaps), sugars, acrylate or acrylate/maleate polymers, sodium silicate, and dicarboxylic acids (for example, Sokalan (Trade Mark) DCS ex BASF).
  • fatty acids or fatty acid soaps
  • sugars acrylate or acrylate/maleate polymers
  • sodium silicate for example, Sokalan (Trade Mark) DCS ex BASF
  • dicarboxylic acids for example, Sokalan (Trade Mark) DCS ex BASF.
  • One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt %.
  • antiredeposition agents such as cellulosic polymers; soil release agents; anti-dye-transfer agents; fluorescers; inorganic salts such as sodium sulphate; enzymes (proteases, lipases, amylases, cellulases); dyes; coloured speckles; perfumes; and fabric conditioning compounds. This list is not intended to be exhaustive.
  • compositions of the invention may be of any suitable physical form, for example, particulates (powders, granules, tablets), liquids, pastes, gels or bars.
  • the detergent composition is in particulate form.
  • Powders of low to moderate bulk density may be prepared by spray-drying a slurry, and optionally postdosing (dry-mixing) further ingredients. “Concentrated” or “compact” powders may be prepared by mixing and granulating processes, for example, using a high-speed mixer/granulator, or other non-tower processes.
  • Tablets may be prepared by compacting powders, especially “concentrated” powders.
  • liquid detergent compositions which may be prepared by admixing the essential and optional ingredients in any desired order to provide compositions containing the ingredients in the requisite concentrations.
  • the polymers may be incorporated at any suitable stage in the manufacture of the compositions of the invention.
  • polymer in powder or solution preferably aqueous form may be incorporated in the slurry.
  • polymer powder or solution may be easily introduced into mixing and granulating apparatus, either alone or in admixture with other solid or liquid ingredients as appropriate.
  • copolymers were prepared by free radical polymerisation. The preparation was adapted from the process described in U.S. Pat. No. 5,319,041 (Zhong et al).
  • the polymers were prepared using a four-step procedure as described below.
  • the relative weights of VP and V2EH required were calculated in function of the % of hydrophobic units needed in the final copolymer. For example, the total quantities required to make a 200 g batch of the polymer of Example 1 as follows:
  • a first mixture was prepared to the following composition:
  • the monomers were charged under a blanket of nitrogen in a 125 mL four-neck flask equipped with a compressed air stirrer, reflux condenser and thermometer. The components were stirred for about 10 minutes and heated to 85° C.
  • Vazo* 67 89.6% of 0.3% of total weight of monomers (VP + V2EH) Luperox* 101 89.6% of 0.3% of total weight of monomers (VP + V2EH) Butanol 2 g was added over a period of 30 minutes.
  • VP 60% of total weight of VP V2EH 75% of total weight of V2EH Butanol 100% of total weight of VP and V2EH of third mixture was then gradually added over a period of 40 minutes.
  • VP 20% of total weight of VP Butanol 100% of weight of VP of fourth mixture was added over a period of 15 min.
  • copolymers were characterised by means of proton NMR spectroscopy and gel permeation chromatography.
  • This formulation has a pH of 7.0. In the doseage 1 g/L and 2 g/L it has a pH of 8.8.
  • the polymers were tested for their ability to enhance the removal of oily and clay/sebum soil from white cotton fabric, using an apparatus for simulating a soiling and wash procedure on a small scale.
  • the fabric was soiled, and subjected to a simulated main wash procedure using wash liquors with and without the polymer according to the invention.
  • the wash apparatus used allows different liquids to be simultaneously contacted with different regions of a single sheet of fabric.
  • the fabric sheet is clamped between an upper and lower block.
  • the fabric sheet is sandwiched between two rubber seals.
  • Both blocks and seals contain an 8 ⁇ 12 array of square cavities, which are aligned.
  • the dry fabric was placed on top of a 96 well polypropylene microtitre plate.
  • Oily soil (5 ⁇ L of dirty motor oil (15% weight in toluene)) was dispensed from a pipette, onto the centre of each of the 96 cells on the cloth.
  • the stained fabrics were allowed to dry at room temperature for 24 hours.
  • test fabric was then clamped in the washing apparatus, 200 ⁇ L doses of each wash solution were placed in appropriate wells.
  • the liquids flowed through the fabrics for 20 minutes, at 30° C. with a flow cycle time of 1.5 seconds. After 20 minutes, the free liquid in the cells was poured off.
  • the blocks where then separated and the fabric removed, and thoroughly rinsed for 1 minute in 200 mL demineralised water. The fabrics were allowed to dry for 24 hours. Reflectance ( ⁇ E or ⁇ R) was then measured.
  • the experiments were carried out at product doses of 0.1, 0.5 and 1.5 g/L, in water of 3° and 12° FH, the hardness being made up of three parts calcium to 1 part magnesium.
  • the polymers were dosed separately at levels of 0.05, 0.1 and 0.5 g/l, and there was also a polymer-free control for each set of conditions.
  • the following table shows the results for all four polymers on oily soil (dirty motor oil) averaged over all product levels (0.1, 0.5 and 1.5 g/l), polymer levels (0.05, 0.1 and 0.5 g/l), and water hardnesses (3 and 12° FH).
  • results are expressed as reflectance increases ( ⁇ R) compared with a control containing no polymer. All results represent a significant difference at 95%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Hydrophobically modified vinyl pyrrolidone polymers which are copolymers having a vinyl pyrrolidone backbone and pendant hydrophobic side chains are useful in laundry detergent compositions to improve detergency and/or antiredeposition. The pendant hydrophobic side chains preferably comprise alkyl chains containing from 4 to 20 carbon atoms and may be linked to the backbone via an ester linkage.

Description

TECHNICAL FIELD
The present invention relates to laundry detergent compositions containing certain vinyl pyrrolidone copolymers. The compositions exhibit improved detergency on oily and clay soils and reduced soil redeposition during the wash.
BACKGROUND AND PRIOR ART
Polyvinyl pyrrolidone (PVP) and some related polymers are known ingredients of laundry detergent compositions, providing the benefit of reduced dye transfer between fabrics in a mixed load.
Laundry detergent compositions containing PVP as a dye transfer inhibitor are disclosed, for example, in WO 92 18597A and WO 95 27028A (Procter & Gamble).
GB 1 354 498 (Unilever) discloses laundry detergent compositions containing vinyl pyrrolidone/vinyl acetate (PVP/VA) random copolymers as antiredeposition agents. PVP itself is stated to be ineffective.
Other vinyl pyrrolidone copolymers are known for cosmetic and agricultural applications.
Definition of the Invention
In a first aspect, the present invention provides a laundry detergent composition comprising an organic surfactant, and a hydrophobically modified vinyl pyrrolidone polymer which is a copolymer having a vinyl pyrrolidone backbone and pendant hydrophobic side chains comprising alkyl chains containing from 4 to 20 carbon atoms, the polymer being present in an amount effective to improve detergency and/or antiredeposition.
In a second aspect, the invention provides the use of a hydrophobically modified vinyl pyrrolidone polymer to improve the detergency and/or antiredeposition of a laundry detergent composition.
The Hydrophobically Modified Vinyl Pyrrolidone Polymer
The polymer used in the detergent compositions of the invention is a polyvinyl pyrrolidone modified by the inclusion of hydrophobic units as pendant side chains. The polymer is a copolymer of vinyl pyrrolidone (VP), providing the polymer backbone, and a hydrophobic monomer.
Vinyl pyrrolidone has the formula
Figure US07160848-20070109-C00001
The hydrophobic side chains preferably comprise alkyl chains containing from 4 to 20 carbon atoms.
First Preferred Embodiment
According to a first preferred embodiment of the invention, the polymer is an alkylated vinyl pyrrolidone polymer wherein the alkyl chains contain from 4 to 20 carbon atoms.
In this embodiment of the invention, the hydrophobic side chains are derived from a hydrophobic comonomer which is an olefin containing from 4 to 20 carbon atoms.
Preferably the polymer contains from 10 to 90 mole % of vinyl pyrrolidone (VP) units and from 10 to 90 mole % of hydrophobic comonomer units.
Suitable polymers are commercially available from International Specialty Products (ISP) as the Ganex (Trade Mark), Antaron (Trade Mark) and Agrimer (Trade Mark) series. They may be prepared by chemical modification of PVP with long-chain alpha-olefins. Examples are shown in the Table below.
Polymer trade Alkyl Comonomer Mole ratio Physical
name chain (olefin) VP:olefin form
Agrimer AL-10 C4 Butene 90:10 Water-
Ganex P904LC soluble
Antaron P904 powder
Ganex V216 C16 Hexadecene 20:80 Water-
Antaron V216 insoluble
wax
Ganex V516 C16 Hexadecene 50:50 Water-
Antaron V516 insoluble
wax
These polymers are marketed for use in cosmetic and personal care compositions, and for agricultural purposes as ingredients in crop treatment compositions.
Second Preferred Embodiment
According to a second preferred embodiment of the invention, the hydrophobically modified vinyl pyrrolidone polymer has pendant hydrophobic side chains which are alkyl chains having from 4 to 20 carbon atoms linked to the vinyl pyrrolidone backbone by an ester linkage.
The hydrophobic monomer precursor of the side chains is preferably a vinyl ester of the general formula I:
R1—CO—O—CH═CH2  (I)
wherein R1 is a linear or branched alkyl group having from 4 to 16 carbon atoms.
In the general formula I, R1 is preferably a linear or branched alkyl group having from 6 to 10 carbon atoms.
More preferably, R1 is a group of the formula II
Figure US07160848-20070109-C00002

wherein R2 is a linear alkyl group having from 2 to 8 carbon atoms and R3 is a methyl or ethyl group.
Most preferably, the hydrophobic comonomer of the formula I is vinyl 2-ethylhexanoate:
Figure US07160848-20070109-C00003
The polymer preferably contains from 90 to 99.5 wt % of vinyl pyrrolidone monomer units and from 0.5 to 10 wt % of vinyl 2-ethyl hexanoate monomer units.
Copolymers of vinyl pyrrolidone and vinyl 2-ethylhexanoate have the general formula III
Figure US07160848-20070109-C00004

Preparation of the Polymers having an Ester Linkage
These polymers may be prepared by free radical polymerisation.
A process suitable for preparing these polymers is disclosed in U.S. Pat. No. 5,319,041 (Zhong et al) which describes the synthesis of copolymers of vinylpyrrolidone and vinyl acetate. An alternative process is disclosed in U.S. Pat. No. 5,122,582 (Porthoff-Karl).
The Laundry Detergent Composition
In the detergent composition of the invention, the polymer is present in an amount sufficient to enhance detergency and/or antiredeposition. Suitably the polymer is present in an amount of from from 0.5 to 5 wt %, preferably from 1 to 4 wt %.
The detergent composition may suitably comprise:
(a) from 5 to 60 wt %, preferably from 10 to 40 wt %, of organic surfactant,
(b) optionally from 5 to 80 wt %, preferably from 10 to 60 wt %, of detergency builder,
(c) from 0.5 to 5 wt %, preferably from 1 to 4 wt %, of the hydrophobically modified vinyl pyrrolidone polymer,
(d) optionally other detergent ingredients to 100 wt %.
The pH of the detergent composition is suitably in the range of from 7.0 to 11.0, preferably 7.5 to 10.5. During the wash in dilute form the pH of the detergent composition is from 7 to 11, preferably from 8.0 to 10.5.
The Organic Surfactant
The compositions of the invention may contain any organic surfactants (detergent-active compounds) suitable for incorporation into laundry detergent compositions.
Detergent-active compounds (surfactants) may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof. Many suitable detergent-active compounds are available and are fully described in the literature, for example, in “Surface-Active Agents and Detergents”, Volumes I and II, by Schwartz, Perry and Berch. The preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds. The total amount of surfactant present is suitably within the range of from 5 to 60 wt %, preferably from 5 to 40 wt %.
Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonaites having an alkyl chain length of C8–C15; primary and secondary alkylsulphates, particularly C8–C20 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium salts are generally preferred. Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8–C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10–C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
Cationic surfactants that may be used include quaternary ammonium salts of the general formula R1R2R3R4N+X wherein the R groups are long or short hydrocarbyl chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising anion (for example, compounds in which R1 is a C8–C22 alkyl group, preferably a C8–C10 or C12–C14 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters).
According to a preferred embodiment of the invention, the composition comprises a sulphonate anionic surfactant. According to an especially preferred embodiment, the sulphonate anionic surfactant comprises linear alkylbenzene sulphonate (LAS).
An especially favourable interaction between LAS and the hydrophobically modified vinyl pyrrolidone polymer has been observed, giving improved primary detergency on difficult oily and particulate soils such as dirty motor oil and mud, and reduced redeposition of soil onto the washload during the wash (sometimes referred to as secondary detergency). Without being bound by theory, it is postulated that the this benefit may be attributed to a reduction in the critical micelle concentration (CMC) of the LAS. Preferably, the compositions contains from 3 to 30 wt %, more preferably from 10 to 25 wt %, of LAS.
The Optional Detergency Builder
Preferably, the detergent compositions of the invention also contain one or more detergency builders. The total amount of detergency builder in the compositions may suitably range from 5 to 80 wt %, preferably from 10 to 60 wt %.
Preferred builders are alkali metal aluminosilicates, more especially crystalline alkali metal aluminosilicates (zeolites), preferably in sodium salt form.
Zeolite builders may suitably be present in a total amount of from 5 to 60 wt %, preferably from 10 to 50 wt %.
The zeolites may be supplemented by other inorganic builders, for example, amorphous aluminosilicates, or layered silicates such as SKS-6 ex Clariant.
The zeolites may be supplemented by organic builders, for example, polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts.
Alternatively, the compositions of the invention may contain phosphate builders, for example, sodium tripolyphosphate.
Especially preferred organic builders are citrates, suitably used in amounts of from 1 to 30 wt %, preferably from 2 to 15 wt %; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt %. Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
According to a preferred embodiment of the invention, the detergency builder, which is present in an amount of from 5 to 80 wt %, preferably from 10 to 60 wt %, is selected from sodium tripolyphosphate, zeolites, sodium carbonate and mixtures thereof.
Other Detergent Ingredients
Detergent compositions according to the invention may also suitably contain a bleach system. Preferably this will include a peroxy bleach compound, for example, an inorganic persalt or an organic peroxyacid, capable of yielding hydrogen peroxide in aqueous solution.
Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate, the latter being especially preferred. The sodium percarbonate may have a protective coating against destabilisation by moisture. The peroxy bleach compound is suitably present in an amount of from 5 to 35 wt %, preferably from 10 to 25 wt %.
The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of from 1 to 8 wt %, preferably from 2 to 5 wt %. Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors. An especially preferred bleach precursor suitable for use in the present invention is N,N,N′,N′-tetracetyl ethylenediamine (TAED).
A bleach stabiliser (heavy metal sequestrant) may also be present. Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA), diethylenetriamine pentaacetate (DTPA), ethylenediamine disuccinate (EDDS), and the polyphosphonates such as the Dequests (Trade Mark), ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphate (DETPMP).
The compositions of the invention may contain alkali metal, preferably sodium, carbonate, in order to increase detergency and ease processing. Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt %, preferably from 2 to 40 wt %.
As previously indicated, sodium silicate may also be present. The amount of sodium silicate may suitably range from 0.1 to 5 wt %. Sodium silicate, as previously indicated, is preferably introduced via the second base granule.
Powder flow may be improved by the incorporation of a small amount of a powder structurant. Examples of powder structurants, some of which may play other roles in the formulation as previously indicated, include, for example, fatty acids (or fatty acid soaps), sugars, acrylate or acrylate/maleate polymers, sodium silicate, and dicarboxylic acids (for example, Sokalan (Trade Mark) DCS ex BASF). One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt %.
Other materials that may be present in detergent compositions of the invention include antiredeposition agents such as cellulosic polymers; soil release agents; anti-dye-transfer agents; fluorescers; inorganic salts such as sodium sulphate; enzymes (proteases, lipases, amylases, cellulases); dyes; coloured speckles; perfumes; and fabric conditioning compounds. This list is not intended to be exhaustive.
Product Form and Preparation
The compositions of the invention may be of any suitable physical form, for example, particulates (powders, granules, tablets), liquids, pastes, gels or bars.
According to one especially preferred embodiment of the invention, the detergent composition is in particulate form.
Powders of low to moderate bulk density may be prepared by spray-drying a slurry, and optionally postdosing (dry-mixing) further ingredients. “Concentrated” or “compact” powders may be prepared by mixing and granulating processes, for example, using a high-speed mixer/granulator, or other non-tower processes.
Tablets may be prepared by compacting powders, especially “concentrated” powders.
Also preferred are liquid detergent compositions, which may be prepared by admixing the essential and optional ingredients in any desired order to provide compositions containing the ingredients in the requisite concentrations.
Incorporation of the Hydrophobically Modified Vinyl Pyrrolidone Polymer
The polymers may be incorporated at any suitable stage in the manufacture of the compositions of the invention.
For example, in the manufacture of spray-dried particulate compositions, polymer in powder or solution (preferably aqueous) form may be incorporated in the slurry. For non-tower particulates, polymer powder or solution may be easily introduced into mixing and granulating apparatus, either alone or in admixture with other solid or liquid ingredients as appropriate.
EXAMPLES
The invention is further illustrated by the following Examples, in which parts and percentages are by weight unless otherwise stated.
Examples 1 to 4
Preparation of vinyl pyrrolidone/vinyl 2-ethylhexanoate Copolymers
The following copolymers were prepared by free radical polymerisation. The preparation was adapted from the process described in U.S. Pat. No. 5,319,041 (Zhong et al).
Weight % Weight %
Example vinyl pyrrolidone vinyl 2-ethyl hexanoate
1 99 1
2 98 2
3 96 4
4 92 8
The starting materials used were as follows (* denotes Trade Mark):
Name Chemical name Supplier Function
VP Vinylpyrrolidone Aldrich Monomer
V2EH Vinyl 2-ethylhexanoate Aldrich Monomer
Vazo* 67 2,2-azobis(2- Fluka Initiator
methylbutyronitrile)
Luperox* 101 2.5-bis(tert-butylperoxy)- Aldrich Initiator
2.5-dimethylhexane
Butanol n-Butanol Solvent

Experimental Procedure
The polymers were prepared using a four-step procedure as described below.
The relative weights of VP and V2EH required were calculated in function of the % of hydrophobic units needed in the final copolymer. For example, the total quantities required to make a 200 g batch of the polymer of Example 1 as follows:
Addition VP VAZO*67 Luperox*101
Step/Reagent (g) V2EH (g) (g) (g) Butanol (g)
1 19.8 0.25 0.0312 0.0312 20.05
2 0.2688 0.2688 2
3 59.4 0.75 60.15
4 19.8 19.8
Total 99   1   0.3   0.3   102
amounts (g)

Four-step Process
A first mixture was prepared to the following composition:
VP   20% of total weight of monomers
V2EH   25% of total weight of monomers
Vazo* 67 10.4% of 0.3% of total weight of monomers
(VP + V2EH)
Luperox* 101 10.4% of 0.3% of total weight of monomers
(VP + V2EH)
Butanol Amount equal to total weight of VP + V2EH in
this mixture
The monomers were charged under a blanket of nitrogen in a 125 mL four-neck flask equipped with a compressed air stirrer, reflux condenser and thermometer. The components were stirred for about 10 minutes and heated to 85° C.
Then a second mixture having the following composition:
Vazo* 67 89.6% of 0.3% of total weight of monomers
(VP + V2EH)
Luperox* 101 89.6% of 0.3% of total weight of monomers
(VP + V2EH)
Butanol 2 g

was added over a period of 30 minutes.
A third mixture of having the following composition:
VP  60% of total weight of VP
V2EH  75% of total weight of V2EH
Butanol 100% of total weight of VP and V2EH of third
mixture

was then gradually added over a period of 40 minutes.
Upon completion of V2EH monomer addition, a fourth mixture having the following composition:
VP  20% of total weight of VP
Butanol 100% of weight of VP of fourth mixture

was added over a period of 15 min.
After the above additions were completed, the temperature was increased to 117° C. for 3 hours. The reactor contents were then cooled to room temperature.
The copolymers were characterised by means of proton NMR spectroscopy and gel permeation chromatography.
Example 5
Detergency/Antiredeposition Performance
Detergency and antiredeposition performance of the polymers were evaluated by a small scale wash method, using a laundry detergent composition having the following formulation:
Weight %
Linear alkylbenzene sulphonate 6.00
Sodium C12–C14 alcohol ethoxy sulphate 3EO 10.50
Nonionic surfactant 6.60
(C12–C14 alcohol ethoxylate, 9EO)
Sodium citrate dihydrate 3.20
Propylene glycol 4.75
Sorbitol 3.25
Sodium borate pentahydrate 2.13
(Water to 100.00)
This formulation has a pH of 7.0. In the doseage 1 g/L and 2 g/L it has a pH of 8.8.
Methodology
The polymers were tested for their ability to enhance the removal of oily and clay/sebum soil from white cotton fabric, using an apparatus for simulating a soiling and wash procedure on a small scale.
Using this apparatus, the fabric was soiled, and subjected to a simulated main wash procedure using wash liquors with and without the polymer according to the invention.
The Apparatus
The wash apparatus used allows different liquids to be simultaneously contacted with different regions of a single sheet of fabric. The fabric sheet is clamped between an upper and lower block. The fabric sheet is sandwiched between two rubber seals. Both blocks and seals contain an 8×12 array of square cavities, which are aligned. When blocks and fabrics are clamped together, liquids placed in individual wells do not leak or bleed through to other wells, due to the pressure applied by the blocks in the regions separating the wells. The liquids are forced to flow back and forth through the fabric by means of a pneumatically actuated thin rubber membrane, which is placed between the fabrics and the lower block. Repeated flexing of the membrane away from and towards the fabrics results in fluid motion through the fabrics.
Soiling
For the oily soil evaluation, the dry fabric was placed on top of a 96 well polypropylene microtitre plate. Oily soil (5 μL of dirty motor oil (15% weight in toluene)) was dispensed from a pipette, onto the centre of each of the 96 cells on the cloth. The stained fabrics were allowed to dry at room temperature for 24 hours.
For clay/sebum soiling a standard cotton test cloth (AS9) was used.
Wash
The test fabric was then clamped in the washing apparatus, 200 μL doses of each wash solution were placed in appropriate wells. The liquids flowed through the fabrics for 20 minutes, at 30° C. with a flow cycle time of 1.5 seconds. After 20 minutes, the free liquid in the cells was poured off. The blocks where then separated and the fabric removed, and thoroughly rinsed for 1 minute in 200 mL demineralised water. The fabrics were allowed to dry for 24 hours. Reflectance (ΔE or ΔR) was then measured.
Experimental Conditions
The experiments were carried out at product doses of 0.1, 0.5 and 1.5 g/L, in water of 3° and 12° FH, the hardness being made up of three parts calcium to 1 part magnesium. The polymers were dosed separately at levels of 0.05, 0.1 and 0.5 g/l, and there was also a polymer-free control for each set of conditions.
For the tests using oily soil (dirty motor oil), the results are expressed as SRI (soil release index), where SRI=100−ΔE
For the tests using clay/sebum soil, the results are expressed as ΔR (image analysis, equivalent to ΔR at 460 nm).
Results for the Polymer of Example 4
Clay/Sebum Soil
ΔR (460 nm) for polymer
Product Water concentrations of
dose Hardness 0
g/L (° F.) (control) 0.05 0.5
0.1 3 4.01 4.13 4.37
0.5 3 3.99 4.36 4.72
1.5 3 4.60 5.44 5.72
0.1 12 3.50 4.00 3.84
0.5 12 3.67 4.01 3.99
1.5 12 3.94 4.36 4.80

Oily Soil (Dirty Motor Oil)
Product Water SRI for polymer concentrations of
dose hardnesS 0
g/L (° F.) (control) 0.05 0.1 0.5
0.1 3 71.31 71.82 71.78 71.92
0.5 3 72.20 72.58 72.21 72.36
1.5 3 72.99 74.01 73.17 73.59
0.1 12 71.16 71.49 71.13 71.88
0.5 12 71.94 72.66 72.14 72.15
1.5 12 73.10 74.49 73.59 74.19

Averaged Results for the Polymers of Examples 1–4
The following table shows the results for all four polymers on oily soil (dirty motor oil) averaged over all product levels (0.1, 0.5 and 1.5 g/l), polymer levels (0.05, 0.1 and 0.5 g/l), and water hardnesses (3 and 12° FH).
The results are expressed as reflectance increases (ΔR) compared with a control containing no polymer. All results represent a significant difference at 95%.
Polymer of Example Mean ΔR
1 0.49
2 0.36
3 0.46
4 0.51

Claims (13)

1. A laundry detergent composition comprising an organic surfactant comprising from 3 to 30% of linear alkylbenzene sulphonate, and a hydrophobically modified vinyl pyrrolidone polymer which is a copolymer having a vinyl pyrrolidone backbone and pendant hydrophobic side chains wherein the pendant hydrophobic side chains of the copolymer are derived from a vinyl ester of the general formula I:

R1—CO—O—CH═CH2  (I)
wherein R1 is a linear or branched alkyl group having from 6 to 10 carbon atoms, the polymer being present in an amount effective to improve detergency and/or antiredeposition.
2. A detergent composition as claimed in claim 1, wherein the polymer contains from 10 to 90 mole % of vinyl pyrrolidone units and from 10 to 90 mole % of hydrophobic comonomer units.
3. A detergent composition as claimed in claim 1, wherein in the general formula I R1 is a group of the formula II
Figure US07160848-20070109-C00005
wherein R2 is a linear alkyl group having from 2 to 8 carbon atoms and R3 is a methyl or ethyl group.
4. A detergent composition as claimed in claim 1, wherein the polymer contains units derived from vinyl 2-ethylhexanoate.
5. A detergent composition as claimed in claim 1, wherein the polymer contains from 90 to 99.5 wt % of vinyl pyrrolidone monomer units and from 0.5 to 10 wt % of vinyl 2-ethylhexanoate monomer units.
6. A detergent composition as claimed in claim 1, which contains from 0.5 to 5 wt % of the hydrophobically modified vinyl pyrrolidone polymer.
7. A detergent composition as claimed in claim 1, which comprises:
(a) from 5 to 60 wt % of organic surfactant,
(b) optionally from 5 to 80 wt %, of detergency builder,
(c) from 0.5 to 5 wt % of the hydrophobically modified vinyl pyrrrolidone polymer,
(d) optionally other detergent ingredients to 100 wt %.
8. A detergent composition as claimed in claim 1 with a pH of from 7.0 to 11.0.
9. A detergent composition as claimed in claim 1, wherein contains from 10 to 25 wt %, of linear alkylbenzene sulphonate.
10. A detergent composition as claimed in claim 1, which comprises from 5 to 80 wt % of detergency builder selected from the group consisting of sodium tripolyphosphate, zeolites, sodium carbonate and mixtures thereof.
11. A method of improving the detergency and/or antiredeposition of a laundry detergent composition, the method comprising incorporating the laundry detergent composition of claim 1 into the composition.
12. A detergent composition is claimed in claim 6 which contains from 1 to 4 wt % of the hydrophobicaily modified vinyl pyrrolidone polymer.
13. Additives and composition as claimed in claim 1 with a pH from 7.5 to 10.5.
US10/734,756 2002-12-13 2003-12-11 Polymers and laundry detergent compositions containing them Expired - Fee Related US7160848B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0229146.6 2002-12-13
GBGB0229146.6A GB0229146D0 (en) 2002-12-13 2002-12-13 Polymers and laundry detergent compositions containing them

Publications (2)

Publication Number Publication Date
US20040127390A1 US20040127390A1 (en) 2004-07-01
US7160848B2 true US7160848B2 (en) 2007-01-09

Family

ID=9949668

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/734,756 Expired - Fee Related US7160848B2 (en) 2002-12-13 2003-12-11 Polymers and laundry detergent compositions containing them

Country Status (14)

Country Link
US (1) US7160848B2 (en)
EP (1) EP1570037B1 (en)
CN (1) CN1753983B (en)
AR (1) AR043709A1 (en)
AT (1) ATE494353T1 (en)
AU (1) AU2003292032A1 (en)
BR (1) BRPI0316725B1 (en)
CA (1) CA2503251C (en)
CL (1) CL2003002615A1 (en)
DE (1) DE60335654D1 (en)
ES (1) ES2359060T3 (en)
GB (1) GB0229146D0 (en)
WO (1) WO2004055147A1 (en)
ZA (1) ZA200504393B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2751578T3 (en) 2015-03-31 2020-04-01 Toray Industries Separation membrane module for medical use, medical device that uses it and blood purifier
DE102015212963A1 (en) * 2015-07-10 2017-01-12 Henkel Ag & Co. Kgaa The primary washing power improving polymeric agents
US10953142B2 (en) * 2016-08-05 2021-03-23 Toray Industries, Inc. Biological component adhesion-suppressing material
JP6958357B2 (en) * 2016-08-31 2021-11-02 東レ株式会社 Medical materials, medical separation membranes, and blood purifiers

Citations (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3557039A (en) 1963-06-05 1971-01-19 Ici Ltd Aqueous dispersion of block or graft polymer useful in surface modifying treatment of polyester shaped articles
DE2165834A1 (en) 1971-12-31 1973-07-05 Henkel & Cie Gmbh Detergents contg vinylpyrrolidone/alkylvinylpyrrolidone - copolymers - as greying inhibitors
DE2165898A1 (en) 1971-12-31 1973-07-05 Henkel & Cie Gmbh ADD DETERGENT WITH AN SCALING PREVENTIVE CONTENT
GB1354498A (en) 1970-08-12 1974-06-05 Unilever Ltd Detergent composition
GB1467098A (en) 1974-06-25 1977-03-16 Procter & Gamble Detergent compositions hving soil release properties
GB1536136A (en) 1975-03-03 1978-12-20 Unilever Ltd Detergent composition
EP0001305A1 (en) 1977-09-23 1979-04-04 THE PROCTER & GAMBLE COMPANY Anionic surfactant-containing detergent compositions having soil-release properties
GB2043082A (en) 1979-02-08 1980-10-01 Oreal Copolymers of n-vinylpyrrolidone and a vinyl allyl or methallyl ester of an or-cyclic carboxylic acid and their use in cosmetics
GB1602420A (en) 1977-05-17 1981-11-11 Oreal Method and compositions for treating the hair and skin based on copolymers carrying tertiary amine and/or quaternary ammonium groups
DE3206883A1 (en) 1982-02-26 1983-09-15 Basf Ag, 6700 Ludwigshafen USE OF COPOLYMERISATES CONTAINING BASIC GROUPS AS GRAY INHIBITORS FOR WASHING AND TREATING TEXTILE MATERIAL CONTAINING SYNTHESIS FIBERS
EP0262945A2 (en) 1986-10-01 1988-04-06 Ciba Specialty Chemicals Water Treatments Limited Water soluble polymeric compositions
EP0271312A2 (en) 1986-12-12 1988-06-15 The Procter & Gamble Company Laundry composition containing peroxyacid bleach and soil release agent
US4846994A (en) 1987-04-03 1989-07-11 Basf Aktiengesellschaft Use of graft polymers based on polyalkylene oxides as grayness inhibitors in the wash and aftertreatment of textile material containing synthetic fibers
US4904408A (en) * 1987-04-03 1990-02-27 Alexander Kud Use of graft polymers based on polyalkylene oxides as grayness inhibitors in the wash and aftertreatment of textile material containing synthetic fibers
EP0403062A2 (en) 1989-06-16 1990-12-19 The Clorox Company Tickened acidic liquid composition with amine fwa useful as a bleaching agent vehicle
WO1991000302A1 (en) 1989-06-26 1991-01-10 Gaf Chemicals Corporation Precipitation polymerization of vinyl lactam terpolymers
WO1992018597A1 (en) 1991-04-12 1992-10-29 The Procter & Gamble Company Compact detergent composition containing polyvinylpyrrolidone
WO1994003567A2 (en) 1992-08-03 1994-02-17 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrrolidone
WO1994006354A1 (en) 1992-09-11 1994-03-31 Surgical Innovations I, L.P. Bracelet retractor assembly
WO1994024249A1 (en) 1993-04-19 1994-10-27 Henkel Kommanditgesellschaft Auf Aktien Washing agents which inhibit dye transfer
WO1995003390A1 (en) 1993-07-19 1995-02-02 The Procter & Gamble Company Detergent compositions inhibiting dye transfer in washing
WO1995017496A1 (en) 1993-12-21 1995-06-29 The Procter & Gamble Company Protease containing dye transfer inhibiting compositions
WO1995027028A1 (en) 1994-03-31 1995-10-12 The Procter & Gamble Company Detergent composition
WO1995034627A1 (en) 1994-06-16 1995-12-21 The Procter & Gamble Company Detergent composition containing wool compatible high alkaline proteases
WO1997003166A1 (en) 1995-07-07 1997-01-30 Henkel Kommanditgesellschaft Auf Aktien Colour transfer-inhibiting washing agent
WO1997020021A1 (en) 1995-11-30 1997-06-05 Unilever Plc Detergent compositions containing soil release polymers
EP0786517A1 (en) 1996-01-25 1997-07-30 Unilever N.V. Detergent composition
WO1997042285A1 (en) 1996-05-03 1997-11-13 The Procter & Gamble Company Cotton soil release polymers
US5783616A (en) 1992-07-02 1998-07-21 Chemische Fabrik Stockhausen Gmbh Graft copolymers of unsaturated monomers and sugars, a process for the production and the use thereof
EP0874892A1 (en) 1995-11-30 1998-11-04 Unilever Plc Detergent compositions containing soil release polymers
EP0876819A1 (en) 1997-05-07 1998-11-11 Basf Aktiengesellschaft Use of copolymers of n-vinylpyrrolidone in the preparation of water insoluble compositions
WO1999009359A1 (en) 1997-08-14 1999-02-25 Etc Energietechnik Und Chemie Gmbh & Co. Kg Solar heat powered cooling plant
EP0957156A1 (en) 1998-05-15 1999-11-17 The Procter & Gamble Company Liquid acidic hard surface cleaning composition
EP1019476A1 (en) 1995-11-30 2000-07-19 Unilever Plc Detergent compositions containing soil release polymers
WO2003044146A1 (en) 2001-11-16 2003-05-30 Ashland Inc. Touchless wheel and tire cleaner and methods of application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3711299C2 (en) * 1987-04-03 1995-07-20 Basf Ag Use of graft polymers based on polyvinylpyrrolidone as graying inhibitors in the washing and aftertreatment of textile fibers containing synthetic fibers

Patent Citations (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3557039A (en) 1963-06-05 1971-01-19 Ici Ltd Aqueous dispersion of block or graft polymer useful in surface modifying treatment of polyester shaped articles
GB1354498A (en) 1970-08-12 1974-06-05 Unilever Ltd Detergent composition
DE2165834A1 (en) 1971-12-31 1973-07-05 Henkel & Cie Gmbh Detergents contg vinylpyrrolidone/alkylvinylpyrrolidone - copolymers - as greying inhibitors
DE2165898A1 (en) 1971-12-31 1973-07-05 Henkel & Cie Gmbh ADD DETERGENT WITH AN SCALING PREVENTIVE CONTENT
GB1467098A (en) 1974-06-25 1977-03-16 Procter & Gamble Detergent compositions hving soil release properties
GB1536136A (en) 1975-03-03 1978-12-20 Unilever Ltd Detergent composition
GB1602420A (en) 1977-05-17 1981-11-11 Oreal Method and compositions for treating the hair and skin based on copolymers carrying tertiary amine and/or quaternary ammonium groups
EP0001305A1 (en) 1977-09-23 1979-04-04 THE PROCTER & GAMBLE COMPANY Anionic surfactant-containing detergent compositions having soil-release properties
GB2043082A (en) 1979-02-08 1980-10-01 Oreal Copolymers of n-vinylpyrrolidone and a vinyl allyl or methallyl ester of an or-cyclic carboxylic acid and their use in cosmetics
DE3206883A1 (en) 1982-02-26 1983-09-15 Basf Ag, 6700 Ludwigshafen USE OF COPOLYMERISATES CONTAINING BASIC GROUPS AS GRAY INHIBITORS FOR WASHING AND TREATING TEXTILE MATERIAL CONTAINING SYNTHESIS FIBERS
US4444561A (en) * 1982-02-26 1984-04-24 Basf Aktiengesellschaft Copolymers which contain basic groups and are used as antiredeposition agents in washing and after-treating textile goods containing synthetic fibers
EP0262945A2 (en) 1986-10-01 1988-04-06 Ciba Specialty Chemicals Water Treatments Limited Water soluble polymeric compositions
EP0271312A2 (en) 1986-12-12 1988-06-15 The Procter & Gamble Company Laundry composition containing peroxyacid bleach and soil release agent
US4846994A (en) 1987-04-03 1989-07-11 Basf Aktiengesellschaft Use of graft polymers based on polyalkylene oxides as grayness inhibitors in the wash and aftertreatment of textile material containing synthetic fibers
US4904408A (en) * 1987-04-03 1990-02-27 Alexander Kud Use of graft polymers based on polyalkylene oxides as grayness inhibitors in the wash and aftertreatment of textile material containing synthetic fibers
EP0403062A2 (en) 1989-06-16 1990-12-19 The Clorox Company Tickened acidic liquid composition with amine fwa useful as a bleaching agent vehicle
WO1991000302A1 (en) 1989-06-26 1991-01-10 Gaf Chemicals Corporation Precipitation polymerization of vinyl lactam terpolymers
WO1992018597A1 (en) 1991-04-12 1992-10-29 The Procter & Gamble Company Compact detergent composition containing polyvinylpyrrolidone
US5783616A (en) 1992-07-02 1998-07-21 Chemische Fabrik Stockhausen Gmbh Graft copolymers of unsaturated monomers and sugars, a process for the production and the use thereof
WO1994003567A2 (en) 1992-08-03 1994-02-17 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrrolidone
WO1994006354A1 (en) 1992-09-11 1994-03-31 Surgical Innovations I, L.P. Bracelet retractor assembly
WO1994024249A1 (en) 1993-04-19 1994-10-27 Henkel Kommanditgesellschaft Auf Aktien Washing agents which inhibit dye transfer
WO1995003390A1 (en) 1993-07-19 1995-02-02 The Procter & Gamble Company Detergent compositions inhibiting dye transfer in washing
WO1995017496A1 (en) 1993-12-21 1995-06-29 The Procter & Gamble Company Protease containing dye transfer inhibiting compositions
WO1995027028A1 (en) 1994-03-31 1995-10-12 The Procter & Gamble Company Detergent composition
WO1995034627A1 (en) 1994-06-16 1995-12-21 The Procter & Gamble Company Detergent composition containing wool compatible high alkaline proteases
WO1997003166A1 (en) 1995-07-07 1997-01-30 Henkel Kommanditgesellschaft Auf Aktien Colour transfer-inhibiting washing agent
EP1019476A1 (en) 1995-11-30 2000-07-19 Unilever Plc Detergent compositions containing soil release polymers
WO1997020021A1 (en) 1995-11-30 1997-06-05 Unilever Plc Detergent compositions containing soil release polymers
EP0874892A1 (en) 1995-11-30 1998-11-04 Unilever Plc Detergent compositions containing soil release polymers
EP0786517A1 (en) 1996-01-25 1997-07-30 Unilever N.V. Detergent composition
WO1997042285A1 (en) 1996-05-03 1997-11-13 The Procter & Gamble Company Cotton soil release polymers
US6075107A (en) 1997-05-07 2000-06-13 Basf Aktiengesellschaft Use of copolymers of N-vinylprrolidone in preparations of water-insoluble substances
EP0876819A1 (en) 1997-05-07 1998-11-11 Basf Aktiengesellschaft Use of copolymers of n-vinylpyrrolidone in the preparation of water insoluble compositions
WO1999009359A1 (en) 1997-08-14 1999-02-25 Etc Energietechnik Und Chemie Gmbh & Co. Kg Solar heat powered cooling plant
EP0957156A1 (en) 1998-05-15 1999-11-17 The Procter & Gamble Company Liquid acidic hard surface cleaning composition
WO2003044146A1 (en) 2001-11-16 2003-05-30 Ashland Inc. Touchless wheel and tire cleaner and methods of application

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
Co-pending U.S. Appl. No. 10/735,376, filed Dec. 11, 2003, Claesson et al.
Derwent Abstract of DE 2 165 898-Dec. 31, 1971.
Derwent Abstract of WO 94/24249-Oct. 27, 1994.
Derwent Abstract of WO 97/03166-Jan. 30, 1997.
Derwent Abstract of WO 99/09359-Feb. 25, 1999.
Derwent Abstract of WO 99/09359-published Feb. 25, 1999.
GB Search Report in a GB application GB 0229146.6.
GB Search Report in a GB application GB 0229147.4.
PCT International Search Report in a PCT application PCT/EP 03/12797.
PCT International Search Report in a PCT application PCT/EP 03/12823.

Also Published As

Publication number Publication date
EP1570037A1 (en) 2005-09-07
BR0316725A (en) 2005-10-18
CA2503251A1 (en) 2004-07-01
CA2503251C (en) 2012-03-27
CL2003002615A1 (en) 2005-04-08
DE60335654D1 (en) 2011-02-17
AU2003292032A1 (en) 2004-07-09
ES2359060T3 (en) 2011-05-18
US20040127390A1 (en) 2004-07-01
EP1570037B1 (en) 2011-01-05
BRPI0316725B1 (en) 2015-10-27
CN1753983A (en) 2006-03-29
ATE494353T1 (en) 2011-01-15
GB0229146D0 (en) 2003-01-15
WO2004055147A8 (en) 2004-10-07
AR043709A1 (en) 2005-08-10
ZA200504393B (en) 2006-08-30
CN1753983B (en) 2010-09-08
WO2004055147A1 (en) 2004-07-01

Similar Documents

Publication Publication Date Title
US7078373B2 (en) Laundry detergent composition
US7160947B2 (en) Polymers and laundry detergent compositions containing them
EP1305387B1 (en) Coloured speckle composition and particulate laundry detergent compositions containing it
EP1272599B1 (en) Laundry wash compositions
US7160848B2 (en) Polymers and laundry detergent compositions containing them
US6573229B2 (en) Laundry wash compositions
US6274664B1 (en) Dye-transfer-inhibiting compositions and particulate detergent compositions containing them
EP1527155B1 (en) Detergent compositions
EP1146110B1 (en) Use of polymers in laundry cleaning
EP1527154B1 (en) Detergent compositions
EP1238052B1 (en) Detergent compositions
US20030166491A1 (en) Detergent composition in tablet form
EP1583814B1 (en) Detergent compositions
EP1623002B1 (en) Detergent compositions
WO2000002985A1 (en) Dye-transfer-inhibiting compositions and particulate detergent compositions containing them

Legal Events

Date Code Title Description
AS Assignment

Owner name: UNILEVER HOME & PERSONAL CARE USA, DIVISION OF CON

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MACNAB, DONNA;SORET, CATHERINE MARIE-JOSEPH SIMONE;THOMAS, ROBERT KEMEYS;AND OTHERS;REEL/FRAME:014494/0156;SIGNING DATES FROM 20031114 TO 20031212

FEPP Fee payment procedure

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

AS Assignment

Owner name: THE SUN PRODUCTS CORPORATION, CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CONOPCO, INC.;REEL/FRAME:023065/0691

Effective date: 20090723

Owner name: THE SUN PRODUCTS CORPORATION,CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CONOPCO, INC.;REEL/FRAME:023065/0691

Effective date: 20090723

FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: U.S. BANK NATIONAL ASSOCIATION, NORTH CAROLINA

Free format text: SECOND LIEN GRANT OF SECURITY INTEREST IN PATENT RIGHTS;ASSIGNORS:SPOTLESS HOLDING CORP.;SPOTLESS ACQUISITION CORP.;THE SUN PRODUCTS CORPORATION (F/K/A HUISH DETERGENTS, INC.);REEL/FRAME:029816/0362

Effective date: 20130213

AS Assignment

Owner name: THE SUN PRODUCTS CORPORATION (F/K/A HUISH DETERGENTS, INC.), UTAH

Free format text: RELEASE BY SECURITY PARTY AS PREVIOUSLY RECORDED ON REEL 029816 FRAME 0362;ASSIGNOR:U.S. BANK NATIONAL ASSOCIATION;REEL/FRAME:030080/0550

Effective date: 20130322

Owner name: THE SUN PRODUCTS CORPORATION (F/K/A HUISH DETERGEN

Free format text: RELEASE BY SECURITY PARTY AS PREVIOUSLY RECORDED ON REEL 029816 FRAME 0362;ASSIGNOR:U.S. BANK NATIONAL ASSOCIATION;REEL/FRAME:030080/0550

Effective date: 20130322

Owner name: SPOTLESS HOLDING CORP., UTAH

Free format text: RELEASE BY SECURITY PARTY AS PREVIOUSLY RECORDED ON REEL 029816 FRAME 0362;ASSIGNOR:U.S. BANK NATIONAL ASSOCIATION;REEL/FRAME:030080/0550

Effective date: 20130322

Owner name: SPOTLESS ACQUISITION CORP., UTAH

Free format text: RELEASE BY SECURITY PARTY AS PREVIOUSLY RECORDED ON REEL 029816 FRAME 0362;ASSIGNOR:U.S. BANK NATIONAL ASSOCIATION;REEL/FRAME:030080/0550

Effective date: 20130322

AS Assignment

Owner name: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT, TEXAS

Free format text: SECURITY AGREEMENT;ASSIGNOR:THE SUN PRODUCTS CORPORATION;REEL/FRAME:030100/0687

Effective date: 20130322

Owner name: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT

Free format text: SECURITY AGREEMENT;ASSIGNOR:THE SUN PRODUCTS CORPORATION;REEL/FRAME:030100/0687

Effective date: 20130322

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20150109

AS Assignment

Owner name: THE SUN PRODUCTS CORPORATION, CONNECTICUT

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:JPMORGAN CHASE BANK, N.A.;REEL/FRAME:040027/0272

Effective date: 20160901

AS Assignment

Owner name: HENKEL IP & HOLDING GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:THE SUN PRODUCTS CORPORATION;REEL/FRAME:041937/0131

Effective date: 20170308